ES2409088T3 - Liquid detergent that inhibits grating - Google Patents

Abstract

Aqueous liquid detergent containing surfactant and other usual ingredients of washing and cleaning products and methyl carboxymethyl cellulose with a degree of methylation in the range of 0.01 to 0.3.

Description

Liquid detergent that inhibits grating

The present invention relates to a liquid detergent that carries surfactants and, as an active substance inhibiting grating, certain cellulose derivative.

Grating inhibitors have the mission of keeping the dirt detached from the fibers suspended in the bathroom when washing the tissues, thus preventing dirt from being deposited back into the tissue. Water-soluble colloids, mostly organic in nature, for example glue, gelatin, starch or cellulose ether sulphonate salts or salts of acidic cellulose or starch sulfates are suitable for this. Water-soluble polyamides containing acidic groups also serve this purpose. Also soluble preparations of starch and other starch products other than those mentioned above may be used, for example degraded starch, aldehyde-starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, methylcarboxymethyl cellulose and mixtures thereof, usually in amounts of 0.1 to 5% by weight with respect to the detergent.

Although said cellulose ethers have a good inhibitory effect of grayness, their use in aqueous liquid detergents is so narrowly limited that in practice they cannot be incorporated into them. Except for their important inhibitory effect of grating, which is only manifested when used in the washing process, these cellulose ethers have a relatively low solubility in surfactant systems and a strong thickening effect in aqueous systems. If aqueous, and specifically anionic, liquid detergents are incorporated in the desired concentrations for the inhibitory effect of graying, products that cannot flow or cannot be poured are usually obtained, whose handling by the user is only feasible by additional work , for example, preparation in water-soluble or water-insoluble single-dose portions and packaged in tear-off bags, or else cellulose ethers do not dissolve completely in aqueous liquid detergents, especially after a long storage period, which In addition to the unsightly appearance, it results in irregular dosing of the grating inhibitor when using the product that contains it.

It has now surprisingly been found that it is possible to achieve a good inhibitory effect of graying in aqueous liquid detergents, without increases in viscosity or unacceptable precipitation, when methylcarboxymethylcellulose with low degree of methylation is used.

The object of the present invention is an aqueous liquid detergent containing surfactant and, if necessary, other usual washing and cleaning components, in which the methyl carboxymethyl cellulose has a degree of methylation in the range of 0.01 to 0 , 3, especially from 0.05 to 0.2. This means that in the cellulose derivative there is on average 0.01 to 0.3, especially 0.05 to 0.2 methyl groups per monomeric unit of anhydroglucose. The degree of carboxymethylation, which indicates the average number of carboxymethyl groups per monomeric unit of anhydroglucose, is preferably in the range of 0.3 to 1, especially 0.4 to 0.8. The average molar mass of the cellulose derivatives used in the present invention is preferably in the range of 80,000 D to 300,000 D, especially 100,000 D to 280,000 D and, especially preferably, in the range of 150,000 D to 250,000 D The determination of the degree of polymerization or the molecular weight of the cellulose ether can be based on the measurement of the limit viscosity index in sufficiently diluted aqueous solutions, by means of a Ubbelohde capillary viscometer (eg capillary 0c). Hence the degree of polymerization can be calculated, as well as the corresponding molecular weight, taking into account the degree of substitution.

Suitable methyl carboxymethyl cellulose according to the present invention can be obtained by the usual route, reacting cellulose with methylating agents such as, for example, chloromethane, and then with carboxymethylation agents such as, for example, chloroacetic acid, using corresponding molar equivalents.

A product according to the present invention preferably contains 0.1% by weight to 2% by weight, especially 0.3% to 1.5% by weight of said methyl carboxymethyl cellulose.

The present invention also relates to the use of said methyl-carboxymethyl cellulose little methylated in aqueous liquid detergents, to improve the inhibition of grating by washing with them flat-structure textile products.

The detergent of the present invention, in addition to said cellulose derivative and other surfactants described below in more detail, contains, with respect to the total product, an amount of water of up to 85% by weight preferably and especially 40% by weight up to 75 % by weight which, if desired, can also be partially replaced by a water-soluble solvent component. The non-aqueous solvents that can be used in liquid products come, for example, from the group of mono- or polyvalent alcohols, alkanolamines or glycol ethers, provided that they are miscible with water within the indicated concentration range. The solvents are preferably chosen from ethanol, n- or ipropanol, butane, ethylene glycol, butanediol, glycerin, diethylene glycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propylene ether, ethylene glycol methyl ether, diethyl ether, diethylene

propylene glycolmethyl-, -ethyl- or -propyl ether, dipropylene glycolmonomethyl- or -ethyl ether, di-isopropylene glycolmonomethyl or -ethyl ether, methoxy-, ethoxy- or butoxytriglycol, 1-butoxy-ethoxy-2-propanol, 3-methyl-3-methoxybutanol -t-butyl ether, as well as mixtures of them. The amount of water-soluble non-aqueous solvent component, with respect to the total amount of washing or cleaning product, is preferably up to 15% by weight, especially 0.5% by weight to 10% by weight.

Liquid detergents contain surfactants, which can be anionic, nonionic, cationic and / or amphoteric. The presence of anionic surfactants is preferred, although mixtures of anionic and non-ionic surfactants are especially advantageous from the point of view of the technical application. The total surfactant content in the liquid product is preferably in the range of 10% by weight to 60% by weight, especially from 15% by weight to 50% by weight, relative to the total liquid product.

As non-ionic surfactants, preferably alkoxylalkoxylates, that is to say alcohols, especially primary, alkoxylated, advantageously ethoxylated, preferably from 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, are used. which the alcohol residue can be linear or, preferably, branched with methyl in position 2 or contain linear and branched radical residues with methyl in the mixture, as is usually the case with the oxoalcohol residues. However, alcoholetoxylates with linear residues of naturally occurring alcohols of 12 to 18 C atoms are preferred - for example coconut, palm, sebacic alcohol, oleyl alcohol - and on average 2 to 8 EO per mole of alcohol . Among the ethoxylated alcohols, for example C12-14 alcohols with 3 EO, 4 EO or 7 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO are preferred , C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as those of C12-14 alcohol with 3 EO and C2-18 alcohol with 7 EO. The degrees of ethoxylation indicated represent statistical mean values, which for a special product can be a whole or fractional number. Preferred alcoholetoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. As an example of this, sebacic alcohol with 14 EO, 25 EO, 30 EO or 40 EO should be mentioned. Also, according to the present invention, nonionic surfactants that together carry EO and PO groups in the molecule can be used. In this case, block copolymers with EO-PO or PO-EO units, as well as EO-PO-EO and PO-EO-PO copolymers can be used. Alkoxylated non-ionic mixed type surfactants can also be used, in which the EO and PO units are not block distributed, but statistically. These products can be obtained by the simultaneous action of ethylene oxide and propylene on fatty alcohols.

In addition, alkylglycosides of the general formula RO (G) x can also be used as non-ionic surfactants, in which R means a primary aliphatic radical of 8 to 22, preferably 12 to 18 C atoms, linear or branched with methyl, specifically in position 2, and the symbol G represents a glycosidic unit of 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably between 1.2 and 1.4.

Another class of nonionic surfactants used preferably - either as a single nonionic surfactant or in combination with other nonionic surfactants - are alkyl esters of alkoxylated fatty acids, especially ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 C atoms. in the alkyl chain and in particular the fatty acid methyl esters.

Non-ionic surfactants of the type of amine oxides can also be used, for example N-coco-alkylN, N-dimethylaminoxide and N-tallow-alkyl-N, N-dihydroxyethylamino oxide. It is preferred that the amount of these non-ionic surfactants is not greater than that of alcoholalkoxylates, in particular half of them.

Other suitable nonionic surfactants are the poly (hydroxylated fatty acid amides) of the formula (I),

where RCO represents an aliphatic acyl radical of 6 to 22 carbon atoms, R1 hydrogen, an alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms and [Z] a linear or branched poly (hydroxyalkyl) radical of 3 to 10 carbon atoms and with 3 to 10 hydroxyl groups. Poly (hydroxylated fatty acid amides) are known substances that can usually be obtained by reductive amination of a reducing sugar with ammonia, with an alkylamine or with an alkanolamine and subsequent acylation with a fatty acid, with an alkyl ester of fatty acid or with a fatty acid chloride. The compounds of the formula (II) also belong to the group of poly (hydroxylated fatty acid amides),

where R represents a linear or branched alkyl or alkenyl radical of 7 to 12 carbon atoms, R1 a linear, branched or cyclic alkyl radical or an aryl radical of 2 to 8 12 carbon atoms and R2 a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical of 1 to 8 12 carbon atoms, with C1-4 alkyl or phenyl radicals being preferred, and [Z] symbolizes a linear poly (hydroxyalkyl) radical whose alkyl chain is substituted with at least two hydroxyl groups , or alkoxylated derivatives, preferably ethoxylated or propoxylated, of this radical. [Z] is preferably obtained by reductive amination of a sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then be transformed into the desired poly (hydroxylated fatty acid amides) by reaction with fatty acid methyl esters, in the presence of an alkoxide as a catalyst.

The content of non-ionic surfactants in liquid detergents is preferably from 5% by weight to 30% by weight, especially from 7% by weight to 20% by weight and, especially preferably, from 9% by weight to 15% by weight. weight with respect to total product. In a preferred embodiment, the non-ionic surfactant is chosen from an alkoxylalkoxylate and an alkyl polyglycoside and mixtures thereof.

As anionic surfactants, for example, those of the sulphonate or sulfate type can be used. The sulphonate-type surfactants preferably include alkyl-C9-13-benzene sulfonates, olefin sulphonates, i.e. mixtures of alkene sulphonates and hydroxyalkane sulphonates, as well as the corresponding disulfonates, such as those obtained, by example, from C12-18 monoolefins with double bond in terminal or internal position by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of sulfonated products. Also suitable are alkane sulphonates that are obtained from C12-18 alkanes, for example by sulphochlorination or sulfoxidation followed by hydrolysis or neutralization. Equally suitable are esters of a-sulfonated fatty acids (sulfonated esters), for example the a-sulfonated methyl esters of coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulphonated fatty acid glyceride esters. Mono-, di- and tri-esters and mixtures thereof are understood as such, obtained by esterification of a monoglycerin with 1 to 3 moles of fatty acid or by transesterification of triglycerides with 0.3 to 2 moles of glycerin. As sulfonated fatty acid glyceride esters, sulfonation products of fatty acids of 6 to 22 carbon atoms are preferred, for example of caproic, caprylic, capric, myristic, lauric, palmitic, stearic or behenic acids.

As alk (en) yl sulfates, alkaline and, in particular, sodium salts of the sulfuric acid half esters of C12-C18 fatty alcohols, for example coconut, tallow, lauric, myristic alcohol alcohols, are preferred. cetyl or stearyl or of the C10-C20 oxoalcohols and the corresponding semi-esters of the secondary alcohols of this chain length. Also preferred are alkyl (en) yl sulfates of said chain length which carry a synthetic linear alkyl radical from a petrochemical manufacturing process and have a degradation type analogous to that of suitable compounds based on fatty chemical raw materials. From the technical point of view of detergency, C12-C16 alkyl sulfates and C12-C15 alkyl sulfates, as well as C14-C15 alkyl sulfates, are interesting and preferred. Also suitable are anionic surfactants are 2,3-alkyl sulfates, such as the products of the Shell Oil Company that can be purchased under the trademark DAN®.

Also suitable are the sulfuric acid monoesters of the above-mentioned alkoxylate alcohol, for example of the C7-21 linear or branched ethoxylated alcohols with 1 to 6 moles of ethylene oxide, such as the C9-11 alcohols branched with 2-methyl which They carry on average 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO, which are often also called ether sulfates.

Other suitable anionic surfactants are the salts of the alkylsulfosuccinic acids, also known as sulfosuccinates or esters of the sulfosuccinic acid, and represented by the monoesters and / or diesters of the sulfosuccinic acid with alcohols, preferably fatty, especially ethoxylated. Preferred sulfosuccinates carry C8-18 fatty alcohol residues or mixtures thereof. Especially preferred sulfosuccinates contain a fatty alcohol residue from ethoxylated fatty alcohols, which in themselves are already non-ionic surfactants (see description below). Sulfosuccinates whose fatty alcohol residues come from ethoxylated fatty alcohols with narrow homolog distribution are also especially preferred here. Likewise, alkyl (en) ilsuccinic acids, preferably from 8 to 18 carbon atoms, can be used in the alkyl (en) alkyl chain.

Preferred anionic surfactants are soaps. Soaps of saturated and unsaturated fatty acids are suitable, such as salts of lauric, myristic, palmitic, stearic, erucic (hydrogenated) and behenic acids and in particular those of natural fatty acids, for example mixtures of acid-derived soaps fatty coconut, palm kernel, olive oil or tallow. In a preferred embodiment the detergent contains 2% by weight up to 20% by weight, especially 3% by weight up to 15% by weight and especially preferably 5% by weight up to 10% by weight of fatty acid soaps. Fatty acid soaps are an important component for the detergency of a liquid, especially aqueous, washing and cleaning product. Surprisingly, it has been shown that by using the poorly methylated carboxymethyl cellulose ether, even in the presence of a large amount of fatty acid soap, transparent and stable liquid detergents are obtained. Normally the use of high amounts (� 2% by weight) of fatty acid soap in these systems results in turbid and / or unstable products.

Anionic surfactants, including soaps, can be found in the form of their sodium, potassium or ammonium salts, and also as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of sodium salts.

The content of anionic surfactants in liquid detergents is preferably from 5% by weight to 35% by weight, especially from 8% by weight to 30% by weight and especially preferably from 10% by weight to 25% by weight with respect to Total product It is especially preferred that the amount of fatty acid soap be at least 2% by weight, especially at least 3% by weight and especially 4% by weight to 10% by weight. In another preferred embodiment, the products contain at least 2, especially 3, anionic surfactants chosen from alkylbenzene sulphonate, ether sulfate and fatty acid soap.

The detergent may contain as a coadjuvant and, if necessary, as a thickener, a polyacrylate. Polyacrylates include polyacrylate or polymethacrylate thickeners, such as homopolymers of high molecular weight acrylic acid crosslinked with a polyalkenyl polyether, especially a sucrose, pentaerythrite or propylene allyl ether (INCI name according to the international dictionary of ingredients cosmetics from “The Cosmetic, Toiletry and Fragrance Association (CTFA)“: Carbomer), also called carboxy-vinyl polymers. These acrylic polyacids can be purchased, among others, from the 3V Sigma firms under the Polygel® trademark, eg Polygel DA, and Noveon with the Carbopol® trademark, eg Carbopol 940 (approximate molecular weight 4,000,000 ), Carbopol 941 (approximate molecular weight 1,250,000) or Carbopol 934 (approximate molecular weight 3,000,000). The following acrylic acid copolymers also belong to this group: (i) copolymers of two or more monomers of acrylic acid, methacrylic acid and its simple esters, preferably formed with C1-4 alkanols (INCI: Acrylates Copolymer), for example the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS number according to the Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3), which can be purchased, by For example, from Rohm & Haas with the trademarks Aculyn® and Acusol® and from Degussa (Goldschmidt) with the trademark Tego® Polymer, eg non-associative anionic polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked acrylic acid copolymers, of high molecular weight, to which the C10-30 alkyl acrylate copolymers with one or more monomers of the group consisting of acrylic acid, methacrylic acid and their simple esters, preferably formed, preferably belong with C1-4 alkanols), crosslinked with a sucrose or pentaerythrite allyl ether (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer), which can be purchased for example from the firm Noveon under the trademark Carbopol®, p. eg Carbopol ETD 2623 hydrophobic and Carbopol 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer), as well as Carbopol Aqua 30 (formerly Carbopol EX 473). Preferred liquid detergents up to 5% by weight, especially from 0.1% by weight to 2.5% by weight polyacrylate. It is advantageous that the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acid with a C10-30 alkyl ester of (meth) acrylic acid.

The viscosity of liquid washing and cleaning products can be measured with the usual standard methods (for example Brookfield LVT-II viscometer at 20 rpm and 20 ° C, spindle 3) and is usually between 150 mPa · s and 5000 mPa · s. Preferred products have viscosities of 500 mPa · s up to 4000 mPa · s, especially preferably 1000 to 3500 mPa · s.

In addition, liquid detergents may contain other auxiliary substances that further improve their technical and / or aesthetic application properties. Within the framework of the present invention, the preferred products contain one or more substances from the group of adjuvants, bleach, bleach activators, enzymes, electrolytes, pH regulators, aromas, perfume vehicles, fluorescent agents, colorants, hydrotropic foam inhibitors , additional dirt repellents or grating inhibitors, optical clarifiers, shrinkage inhibitors, wrinkle protectors, dye transfer inhibitors, antimicrobial agents, germicidal agents, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing preparations, hydrophobic agents and impregnators, swelling and anti-slip agents, as well as UV absorbers.

As adjuvants, the liquid products may contain, in particular, silicates, aluminum silicates (especially zeolites), carbonates, organic salts of di- and polycarboxylic acids, as well as mixtures of these substances.

Suitable crystalline sodium phyllosilicates have the general formula NaMSixO2x + 1 · and H2O, where M means sodium

or hydrogen, x a number from 1.9 to 4 and y a number from 0 to 20, and the preferred values for x are 2, 3 or 4. The preferred crystalline phyllosilicates of the aforementioned formula are those in which M represents sodium and x takes values 2 or 3. Specifically, both �- and sodium a-silicates Na2Si2O5 · and H2O are preferred.

Amorphous sodium silicates can also be used with a Na2O: SiO2 module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and especially 1: 2 to 1: 2.6, which are of delayed dissolution and have secondary detergent properties. The dissolution delay against ordinary amorphous sodium silicates can be induced in two ways, for example by surface treatment, mixing, compaction / compression or over-drying. Within the framework of the present invention the term "amorphous" also includes "amorphous under X-rays." This means that in the X-ray diffraction experiments the silicates do not give the clear reflections characteristic of the

crystalline substances, but at most one or several maximums of the dispersed X radiation having a width of several degrees of the diffraction angle. However, very good results can be achieved as an adjuvant when in the electronic diffraction experiments the silicate particles generate overlapping or even sharp maximums, which should be interpreted as that the microcrystalline products have areas with a size of 10 to a few hundred nm, being preferred maximum values up to 50 nm and especially up to 20 nm. These silicates called amorphous under X-rays also have a delayed dissolution compared to soluble glasses. Especially preferred are compacted / compressed amorphous silicates, compound amorphous silicates and amorphous silicates under the over-X-rays.

Synthetic zeolite of fine crystalline structure containing adsorbed water is preferably zeolite A and / or P. Zeolith P is especially preferred Zeolith MAP® (commercial product of Crosfield). Also suitable is zeolite X and mixtures of A, X and / or P. It can also be purchased commercially and used within the framework of the present invention, for example, a co-crystallized product of zeolite X and zeolite A (with approx. 80% by weight of zeolite X), which is sold by SASOL under the trademark VEGOBOND AX® and can be described by the formula

nNa2O · (1-n) K2O · Al2O3 · (2 - 2.5) SiO2 · (3.5 - 5.5) · H2O

where n = 0.90 - 1.0. The zeolite can be used as a spray-dried powder or even without drying, even wet, from its manufacturing process, in the form of a stabilized suspension. In the case of using the zeolite in suspension, it may contain small additions of non-ionic surfactants as stabilizers, for example 1 to 3% by weight of C12-C18 fatty alcohols with 2 to 5 groups of ethylene oxide, C12- fatty alcohols C14 with 4 to 5 groups of ethylene oxide or ethoxylated isotridecanoles. Suitable zeolites have an average particle size of less than 10 mm (volumetric distribution; measurement method: Coulter counter) and preferably contain 18 to 22% by weight, especially 20 to 22% by weight, of adsorbed water.

As auxiliary substances, generally known phosphates can also be used, unless their use should be avoided for ecological reasons. Sodium salts of orthophosphates, pyrophosphates and, especially, tripolyphosphates are especially suitable.

Among the bleaching compounds that contribute H2O2 to water, sodium perborate tetrahydrate and sodium perborate monohydrate are especially important. Other usable bleaches are, for example, sodium percarbonate, peroxypyrophosphates, citrate-perhydrates, and also salts of peracids or peracids that release H2O2, for example perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminic peracidine or diperdodecanedioic acid. When present they are preferably used in a coated form to protect them from decomposition during storage.

To wash at temperatures of 60 ° C and achieve under these conditions a better bleaching effect, bleach activators can be incorporated into the washing and cleaning products. As bleaching activators, compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids preferably formed by 1 to 10 C atoms, especially 2 to 4 C atoms, and / or, if necessary, substituted perbenzoic acids can be used. Substances bearing O- and / or N-acyl groups of said number of C atoms and / or, if necessary, substituted benzoyl groups are suitable. Polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, are preferred, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonaoyl succinimide (NOSI), acylated phenolsulfonates, especially n-nonaoyl- or isononaoylbenzenesulfonate (n- o. iso-NOBS), the anhydrides of carboxylic acid, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to conventional bleaching activators, or instead, so-called bleaching catalysts can also be incorporated into liquid washing and cleaning products. These are substances that reinforce bleaching and are salts or complexes of transition metals such as, for example, complex salts or carbonyl complexes of Mn, Fe, Co, Ru or Mo. As bleaching catalysts, Mn complexes can also be used , Fe, Co, Ru, Mo, Ti, V and Cu with nitrogenous tripod binders, as well as amino complexes of Co, Fe, Cu and Ru.

Enzymes, especially those of the classes of hydrolases, such as proteases, esterases, lipases or enzymes of lipolytic action, amylases, cellulases and other glycosyl hydrolases and mixtures of said enzymes come into consideration. All these hydrolases contribute to the removal of greasy or starchy spots and the gray ones in the laundry. In addition, cellulases and other glycosyl hydrolases can contribute to maintaining color and increasing the softness of the tissue, by eliminating frizz and microfibrils. Oxidoreductases can also be used for bleaching and for the inhibition of dye transfer. Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Preferably, Subtilisin type proteases and, above all, proteases obtained from Bacillus lentus are used. In this case, enzymatic mixtures, for example protease and amylase, are of particular interest; or of protease and lipase or lipolytic enzymes; or of protease and cellulase; or of cellulase and lipase or lipolytic enzymes; or of protease, amylase and lipase or lipolytic enzymes; or of protease, lipase or lipolytic enzymes and cellulase; but especially mixtures containing protease and / or lipase or mixtures with lipolytic enzymes. Are examples

of these enzymes of lipolytic action the known cutinases. In some cases peroxidases or oxidases have also proved suitable. As suitable amylases, mention may be made of a-amylases, iso-amylases, pululanases and pectinases. Cellobiohydrolases, endoglucanases and -glucosidases, also called cellobiases, or mixtures thereof are preferably used as cellulases. As the different types of cellulases can be distinguished by their CMCase and avicelase activities, mixing them properly can adjust the desired activities.

Bleach activators or catalysts and / or enzymes may be adsorbed on support and / or coated substances, in order to protect them from premature decomposition. The content of enzymes, liquid formulations of enzymes or enzymatic granules may be, for example, from about 0.1% by weight to 5% by weight, preferably from 0.12% by weight to 2.5% by weight, based on to the total product.

As electrolytes of the group of inorganic salts, a large number of different salts are available. Preferred cations are alkali and alkaline earth metals; Preferred anions are halides and sulfates. From the technical point of view of production it is preferred to use NaCl or MgCl2 in the products. The electrolyte content in the products does not usually exceed 8% by weight, usually between 0.5% by weight and 5% by weight.

In order to bring the pH of the liquid products to the desired level it may be convenient to use pH regulators. In this case all known acids and bases can be used, unless it is prohibitive for ecological reasons.

or user protection. The amount of these regulators does not usually exceed 10% by weight of the total formulation.

Another component contained in the products of the present invention is, if desired, a hydrotrope. Preferred hydrotropes include those of the sulfonated type, such as alkylaryl sulphonates or alkylarylsulfonic acids. Preferred hydrotropes are chosen from xylene, toluene, cumene, naphthalene sulfonates or between xylene-, toluene-, cumen-, naphthalene sulfonic acids and mixtures thereof. The counterions are preferably chosen from sodium, calcium and ammonium. If necessary, liquid products can contain up to 20% by weight of a hydrotrope, especially between 0.05% by weight and 10% by weight.

To improve the aesthetic impression of liquid products, these can be colored with suitable dyes. Preferred dyes, which the specialist can choose without any difficulty, have great storage stability and are insensitive to the usual ingredients of the products and to light, and have no pronounced substantivity against textile fibers, so as not to dye them .

Suitable foam inhibitors in liquid washing and cleaning products include, for example, soaps, paraffins or silicone oils, which, if necessary, can also be applied to support materials.

As agents for preventing redeposition, also called "dirt repellents", suitable are, for example, polymers of phthalic acid and / or terephthalic acid known from the technical state and its derivatives, especially polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or derivatives of them with anionic and / or non-ionic modification. Among them, sulfonated derivatives of phthalic and terephthalic acid polymers are especially preferred.

Optical lighteners can be added to liquid washing and cleaning products to eliminate yellowing of treated textile structures. These substances are fixed in the fibers and produce a bleaching by transforming the ultraviolet radiation, invisible to the human eye, into visible long wave light, so that the ultraviolet light absorbed from sunlight is reflected as weakly blue fluorescence and in combination With the yellow shade of the yellowed wash results in a pure white. Suitable compounds are derived, for example, from the following classes of substances: 4,4'-diamino-2,2'-stilbendisulfonic acids (flavonic acids), 4,4'-diethyrylbiphenylenes, methyl umbelliferones, coumarins, dihydroquinolinones, 1 , 3-diarylpyrazolines, naphthalimides, benzoxazole, benzoisoxazole and benzimidazole systems, as well as heterogeneous substituted pyrene derivatives. The amount of optical lighteners with respect to the final product is usually up to 0.5% by weight, especially from 0.03% by weight to 0.3% by weight.

As flat textile products - especially those of reyon, viscose, cotton and their mixtures - may have a tendency to wrinkle, since the individual fibers are sensitive to bending, bending, compression and crushing in a transverse direction to that of The fibers, the products can wear synthetic wrinkle protectors. These include synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkyl esters, fatty acid alkylamides or fatty alcohols, mostly modified with ethylene oxide, or lecithin-based products or esters modified phosphoric.

To combat microorganisms, liquid washing and cleaning products may carry antimicrobial active ingredients. In this case, according to the antimicrobial spectrum and the mechanism of action, it is necessary to distinguish between bacteriostatic and bactericidal, between fungistatic and fungicidal, etc. As important examples of substances in this group, benzalkonium chlorides, alkylaryl sulphonates, halogenated phenols and phenylmercuriacetate may be mentioned, although these products can also be completely dispensed with.

compounds.

To avoid unwanted alterations due to the effect of oxygen and other oxidative processes in liquid washing and cleaning products and / or in treated tissues, the products may contain antioxidants. To this class of compounds belong, for example, substituted phenols, hydroquinones, pyrocatechins and aromatic amines, as well as organic sulphides, polysulfides, dithiocarbamates, phosphites and phosphonates. When these antioxidants are used, the products of the present invention are naturally free of oxidizing bleaching agents.

The additional use of antistatic products can provide greater comfort to the tissues. Antistatics increase surface conductivity and therefore allow better evacuation of formed charges. In general, external antistatics are substances with at least one hydrophilic ligand molecule and form a more or less hygroscopic film on the surfaces. These antistatics, mostly surfactants, can be classified into nitrogen (amines, amides, quaternary ammonium compounds), phosphorous (phosphoric acid esters) and sulfurized (alkyl sulphonates, alkyl sulfates). External antistatics are, for example, lauryl- (or stearyl-) dimethylbenzyl ammonium chlorides, which are suitable as antistatic for fabrics, or as an additive for detergents, and also have a fanning effect.

In order to improve the water absorption power and the rewetting capacity, and to facilitate the ironing of the treated fabrics, in the liquid washing and cleaning products, for example, silicone derivatives, which also improve the rinsing of detergents thanks to their foam inhibitory properties. Preferred silicone derivatives are, for example, polydialkyl- or alkylarylsiloxanes whose alkyl groups possess one to five C atoms and are totally or partially fluorinated. Preferred silicones are polydimethylsiloxanes that can also be modified and then are amino-functional or quaternized, or have Si-OH-, Si-H- and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C range from 100 to

100,000 mPa · s. Silicones are used in amounts of 0.2 to 5% by weight with respect to the total product.

Finally, liquid washing and cleaning products can also contain UV absorbers that are fixed to the treated tissues, improving the light resistance of the fibers. Compounds that possess these desired characteristics are, for example, benzophenone compounds and derivatives with substituents in position 2 and / or 4, which act by deactivation without radiation emission. Also suitable are substituted benzotriazoles, acrylates substituted with phenyl in position 3 (derivatives of cinnamic acid), occasionally with cyano groups in position 2, salicylates, organic complexes of Ni, as well as natural substances such as umbelliferone and urocanic acid .

To prevent certain detergent ingredients from decomposing due to the catalytic action of heavy metals, heavy metal complexing substances can be used. As complexers of heavy metals, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) are useful, as well as alkali metal salts of anionic polyelectrolytes such as polimaleates and polysulphonates.

A preferred class of complexers are phosphates, which in the preferred liquid products are contained in amounts of 0.01% by weight up to 2.5% by weight, preferably 0.02% by weight up to 2% by weight, and, above all, from 0.03% by weight to 1.5% by weight. To these preferred compounds belong, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acids (HEDP), aminotri (methylene phosphonic) (ATMP), diethylenetriaminopenta (methylene phosphonic) (DTPMP or DETPMP), as well as 2 -phosphonobutan-1,2,4-tricarboxylic (PBS-AM), which are mostly used in the form of their ammonium or alkaline salts.

Liquid detergents are preferably clear, that is, they have no sediment and are transparent or at least translucent. Without the addition of a dye, the washing and cleaning products preferably show a visible light transmission (410 to 800 nm) of at least 30%, especially at least 50% and especially preferably at least 75%.

In addition to said components, a washing and cleaning product may also contain dispersed particles whose diameter along its maximum spatial extent is, for example, from 0.01 µm to 10,000 µm. Said particles may be both microcapsules or specks as granules, compounds and odor beads, with microcapsules or specks being preferred.

The term "microcapsules" refers to aggregates that at least contain a solid or liquid core surrounded by at least one continuous envelope, especially a continuous envelope of polymer (s). In general, they are finely dispersed liquid or solid phases, wrapped by film-forming polymers, during which the polymers precipitate on the material to be wrapped, after emulsion and coacervation or interfacial polymerization. Small microscopic capsules can dry as a powder. In addition to mononuclear microcapsules, polynuclear aggregates are also known, also called microspheres, which contain two or more nuclei distributed throughout the envelope material continuously. Also, the mono- or polynuclear microcapsules can be coated by a second, third, etc. additional wrap Mononuclear microcapsules that carry a continuous envelope are preferred. The envelope can be made of natural, semi-synthetic or synthetic materials. The natural wrapping materials are, for example, gum arabic, agar-agar, agarose, maltodextrin, alginic acid or its salts, eg the

sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes. Semi-synthetic wrapping materials are, among others, chemically modified celluloses, especially cellulose esters and ethers, eg cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, as well as starch derivatives, especially starch esters and esters . Synthetic wrapping materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

Microcapsules may stably include storage and transport components (= active substances) of the liquid product that are sensitive and chemically or physically incompatible. The microcapsules can, for example, contain optical clarifiers, surfactants, complexing agents, bleaching agents, bleaching activators, colorants and perfumes, antioxidants, adjuvants, enzymes, enzyme stabilizers, antimicrobial active ingredients, dirt repellents, pH regulators , electrolytes, foam inhibitors and / or UV absorbers. In addition to the components of the aqueous liquid products of the present invention cited above, the microcapsules may contain, for example, vitamins, proteins, preservatives, wash-enhancing additives or adolescent agents. The microcapsule fillers can be solid or liquid in the form of solutions, emulsions or suspensions.

Depending on their processing conditions, the microcapsules can have any shape, although preferably they are almost spherical. Its diameter along its maximum spatial extent can vary between 0.01 µm (at a glance not recognizable as a capsule) and 10,000 µm, depending on the components it contains and according to its application. Visible microcapsules with a diameter between 100 and 7,000 µm are preferred. The microcapsules can be made by processes known in the technical state, among which coacervation and interfacial polymerization are of the greatest importance. As microcapsules, all those offered on the market can be used as stable microcapsules for surfactants, for example commercial products (in parentheses the respective wrapping material) Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (marine collagen), Lipotec Millicapseln ( alginic acid, agar-agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids) modified agar) and Kuhs Probiol Nanospheres (phospholipids).

Alternatively, particles without any core-shell structure can be used, in which the active substance is distributed in a material that forms a matrix. These particles are also designated as "motes." A preferred material for forming the matrices is alginate. To produce alginate-based specks, an alginate solution is also dripped that also contains the active substance (s) to be included and then hardened in a precipitation bath containing free Ca2 + or Al3 + ions. It may be advantageous to subsequently wash the alginate specks with water and then in an aqueous solution with a complexing agent, in order to eliminate free Ca2 + or Al3 + ions that could produce unwanted interactions with ingredients of the washing and cleaning liquid product, e.g. with fatty acid soaps. Then the alginate spots are washed with water to remove excess complexing. As an alternative, other matrix forming materials can also be used instead of alginate; Examples include: polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, acrylic polyacid, poly (ethylene oxide), polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextranyl, Ficolipulidulose, hydroxyl cellulose hydroxypropylmethylcellulose, hyaluronic acid, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. Matrix formation with these materials takes place, for example, by gelation, by polyanion-polycation or polyelectrolyte-ion metal interactions and - as well as the preparation of particles with these matrix-forming materials - is well known in the technical state. The particles can be dispersed stably in the aqueous liquid washing and cleaning products. Stable means that the products are stored at room temperature and at 40 ° C for a minimum time of 4 weeks, preferably at least 6 weeks, without cream or settling.

The release of the active substances from the microcapsules or the specks normally takes place during the use of the products that contain them, by decomposition of the envelope or the matrix due to the mechanical, thermal, chemical or enzymatic effect. In a preferred embodiment of the present invention liquid detergents carry equal or different particles in amounts of 0.01 to 10% by weight, especially 0.2 to 8% by weight and especially 0.5 to 5% by weight.

Aqueous liquid washing and cleaning products can be manufactured economically and easily in common mixing and packaging facilities. In order to produce the liquid products, the acidic components, such as linear alkyl sulphonates, citric, boric, phosphonic acids, fatty alcohol ether sulfates and non-ionic surfactants, are first introduced. Solvents are also incorporated at this time, but can be added later. To these components are added, if any, the complexing agent. Then a base is added, such as NaOH, KOH, triethanolamine or monoethanolamine, and then, if any, fatty acids. The other ingredients are then added to the mixture and, if necessary, the remaining solvents of the aqueous liquid product and the pH is adjusted to the desired value. Finally, if desired, the particles to be dispersed can be added, mixing them homogeneously in the aqueous liquid products.

Examples Table 1 shows the composition (percentage by weight of ingredients with respect to the total product) of detergents M1 and M2 according to the present invention. Table 1:

M1

 M2

C9-13 alkyl benzosulfonate, Na salt

10 10

Sodium lauryl ether sulfate with 2 EO

5 5

C12-14 fatty alcohol with 7 EO

10 10

C12-14 alkylglycoside

 2 2

C12-18 fatty acid, Na salt

8 8

Glycerin

5 5

Trisodium citrate

one one

Polyacrylate

2 2

Me-CMC Ia)

one -

Me-CMC IIb)

- one

Enzymes, dye, optical lighter

Water

up to 100 up to 100

a) Methylation degree 0.09, carboxymethylation degree 0.56, molecular mass 218,000 b) Methylation degree 0.14, carboxymethylation degree 0.73, molecular mass 198,000

10 Products were tested under the following conditions:

Washing machine: Launderometer, from Atlas Bolas: 10 Washing temperature: 40ºC, 60 min.

15 Determination: triple Number of washes: 5 Bath ratio: 1: 12 Water hardness: 16º dH Dirt support: 6.7 g of gray fabric sample

20 Dosage: 1 g of product / 200 ml

The following materials were used:

At 65% polyester / 35% cotton, WFK 20A

25 B 100% cotton Trigema® Jersey, pink C 100% cotton, Trigema® piqué, light yellow D 100% cotton, twisted curly fabric, 1.1.04, white with optical clarifier E 100% cotton, gender cotton knit, 1.1.27, double ribbed, bleached, with F 100% cotton optical lightening, cotton fabric, WFK 10A, without optical lightening

30 Table 2 shows the percentage improvement in the inhibition of grayness, resulting from the use of methylated carboxymethylcelluloses with a low degree of methylation (compared to another product of the same composition that lacked this active substance).

35 Table 2:

M1

M2

TO

5.5 4.6

B

5.6 7.3

C

 12.0 10.1

D

 10.4 10.5

AND

17.4 13.6

F

11.4 11.3

Claims (8)

1. Aqueous liquid detergent containing surfactant and other usual ingredients of washing products and cleaning and methyl carboxymethyl cellulose with a degree of methylation in the range of 0.01 to 0.3. 5 2. Product according to claim 1, characterized in that the methyl carboxymethyl cellulose has a carboxymethylation grade of 0.3 to 1, especially 0.4 to 0.8. 3. Product according to claim 1 or 2, characterized in that the methyl carboxymethyl cellulose has a degree of methylation in the range of 0.05 to 0.2. 4. Product according to one of claims 1 to 3, characterized in that it contains 0.1% by weight to 2% by weight, especially 0.3% by weight to 1.5% by weight of the methyl carboxymethyl cellulose. Product according to one of claims 1 to 4, characterized in that it contains 10% by weight up to 60% by weight, especially 15% by weight up to 50% by weight of surfactant. 6. Product according to one of claims 1 to 5, characterized in that it contains anionic surfactant and in Concrete fatty acid soap. twenty 7. Product according to one of claims 1 to 6, characterized in that it contains at least 2 different surfactants, chosen from alkylbenzene sulphonate, ether sulfate and soap. 8. Product according to one of claims 1 to 7, characterized in that it contains non-ionic surfactant, specifically chosen from alcoholalkoxylate and alkyl polyglycoside and mixtures thereof. 9. Product according to one of claims 1 to 8, characterized in that it contains up to 85% by weight, especially 40% by weight up to 75% by weight of water. 30 10. Use of methyl carboxymethyl cellulose with a degree of methylation in the range of 0.01 to 0.3 in aqueous liquid detergents, to improve the inhibition of grating during the washing of textile products.